Towards attochemistry: Control of nuclear motion through conical intersections and electronic coherences

Abstract

The effect of nuclear dynamics and conical intersections on electronic coherences is investigated employing a two-state, two-mode linear vibronic coupling model. Exact quantum dynamical calculations are performed using the multi-configuration time-dependent Hartree method (MCTDH). It is found that the presence of a non-adiabatic coupling close to the Franck-Condon point can preserve electronic coherence to some extent. Additionally, the possibility of steering the nuclear wavepackets by imprinting a relative phase between the electronic states during the photoionization process is discussed. It is found that the steering of nuclear wavepackets is possible given that a coherent electronic wavepacket embodying the phase difference passes through a conical intersection. A conical intersection close to the Franck-Condon point is thus a necessary prerequisite for control, providing a clear path towards attochemistry.